Insecticidal and acaricidal 1-phenyl-1-P-propargyloxyphenyl-2-nitroethanes

ABSTRACT

1-Phenyl-1-p-propargyloxyphenyl-2-nitro-ethane derivatives of the formula ##STR1## wherein Z represents the radical ##STR2## and of the symbols 
     X and Y one represents hydrogen, fluorine, chlorine, bromine, C 1  -C 3  -alkyl, C.sub. 1 -C 3  -alkoxy, propargyloxy or C 1  -C 3  -alkylthio, and the other represents propargyloxy, 
     Process for their preparation and their use in pest control.

This is a division of application Ser. No. 437,417 filed on Jan. 28,1974 now U.S. Pat. No. 3,950,433. su

The present invention relates to1-phenyl-1-p-propargyloxyphenyl-2-nitroethane derivatives, to processesfor their preparation, and to their use in pest control.

The said 1-phenyl-1-p-propargyloxyphenyl-2-nitroethane derivatives havethe formula ##STR3## wherein Z represents the radical ##STR4## and ofthe symbols X and Y one represents hydrogen, fluorine, chlorine,bromine, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, propargyloxy or C₁ -C₃-alkylthio, and the other represents propargyloxy.

The alkyl, alkoxy or alkylthio groups denoted by X or Y can bestraight-chain or branched-chain. Such groups are: methyl, methoxy,methylthio, ethyl, ethoxy, ethylthio, n-propyl, n-propoxy, n-propylthio,isopropyl, isopropoxy or isopropylthio.

Compounds of formula I preferred on account of their action are thosewherein

Z represents the radical ##STR5## and of the symbols X and Y onerepresents hydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, propargyloxy or C₁-C₃ -alkylthio, and the other represents propargyloxy.

Particularly preferred, however, are compounds of formula I wherein

Z represents the radical ##STR6## and of the symbols X and Y onerepresents hydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy or propargyloxy, andthe other represents propargyloxy, and the other representspropargyloxy.

The compounds of formula I can be prepared, e.g. analogously to thefollowing known method: ##STR7## Applicable condensation agents areinorganic acids such as sulphuric acid; organic acids such as aceticacid; Lewic acids such as aluminium chloride or boron trifluoride in theform of complexes with inorganic or organic acids, such as phosphoricacid, acetic acid, etc..

The reaction is performed under normal pressure, at a temperature ofbetween -30° and +100° C, preferably between 0° and 40° C, andoptionally in solvents such as, e.g. acetic acid, nitroalkanes ormethylene chloride.

The starting materials of formula II are in part known, or can beprepared by methods analogous to known methods, e.g. analogous to thosedescribed in the U.S. Pat. No. 2,516,186.

The compounds of formula I have a broad biocidal action, and can be usedfor the control of various plant and animal pests.

Compared with analogous compounds, the compounds of formula I have asurprisingly better insecticidal action, particularly against Spodopteralitoralis, a toxicity level suitable for application and betterdecomposability.

The action of the compounds according to the invention extends moreoverto all development stages, such as eggs, larvae, nymphs, pupae andadults of insects of the families: Aerididae, Blattidae, Gryllidae,Cryllotalpidae, Tettigoniidae, Cimiciade, Phyrrhocoridae, Reduviidae,Aphidiae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae,Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae,Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae,Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Culicidae, Trypetidaeand Pulicidae, as well as acarids of the families: Ixodidae, Argasidaeand Dermanyssidae.

The insecticidal or acaricidal action can be appreciably widened andadapted to suit given circumstances by the addition of otherinsecticides and/or acaricides. Suitable additives are, e.g. thefollowing active substances:

organic phosphorus compounds, nitrophenols and their derivatives,formamidines, ureas, carbamates and chlorinated hydrocarbons. piperonyl

The compounds of formula I are combined with particular advantage withsubstances having a synergistic or intensifying effect. Examples of suchcompounds are pyrethrin synergists such as piperonly butoxide orZ-(3,4-methylenedioxyphenoxy)-3,6,9-trioxa-undecane (Sesoxane).

The compounds of formula I can be used on their own or together withsuitable carriers and/or additives. Suitable carriers and additives maybe solid or liquid, and they correspond to the substances common informulation practice, such as, e.g. natural and regenerated substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

For application, the compounds of formula I can be processed into theform of dusts, emulsion concentrates, granulates, dispersions, sprays,or solutions, the formulation of these preparations being effected to amanner commonly known in practice. Also to be mentioned are cattle dipsand spray races, in which aqueous preparations are used.

The agents according to the invention are produced in a manner known perse by the intimate mixing and/or grinding of active substances offormula I with suitable carriers, optionally with the addition ofdispersing agents or solvents which are inert to the active substances.The active substances can be obtained and used in the following forms:

solid preparations:

dusts, scattering agents, granulates coated granulates, impregnatedgranulates and homogeneous granulates;

liquid preparations:

a. water dispersible active-substance concentrates: wettable powders,pastes, emulsions;

b. solutions.

The content of active substance in the described agents is between 0.1and 95%; it is to be mentioned in this connection that in the case ofapplication from an aeroplane, or by means of other suitable devices,concentrations of up to 99.5% can be employed, or even the pure activesubstance.

The active substances of formula I can be prepared, for example, asfollows:

Dusts:

The following substances are used in the preparation of (a) a 5% dust,and (b) a 2% dust:

a. 5 parts of active substance,

95 parts of talcum;

b.

2 parts of active substance,

1 part of highly dispersed silicic acid,

97 parts of talcum

The active substances are mixed and ground with the carriers.

Granulate:

The following substances are used to produce a 5% granulate:

5 parts of active substance,

0.25 parts of epichlorhydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 - 0.8 mm).

The active substance is mixed with epichlorhydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The solution thus obtained is sprayed on to kaolin, and theacetone subsequently evaporated off in vacuo.

Wettable powder:

The following constituents are used for the preparation of (a) a 40%,and (b) and (c) a 25%, and (d) a 10% wettable powder:

a.

40 parts of active substance,

5 parts of sodium lignin suplhonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silici acid.

b.

25 parts of active substance.

4.5 parts of calcium lignin sulphonate

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silici acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c.

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene-ethane

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts sodium aluminium silicate,

16.3 parts of kieselguhr,

46 parts of Kaolin

d.

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde, condensate.

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to produce (a) a 10% and (b) a 25%emulsifiable concentrate:

a.

10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylaryl-sulphonate calcium salt.

40 parts of dimethylformamide,

43.2 parts of xylene.

b.

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcohol-polyglycol ethermixture

5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorhydrin,

94 parts of ligroin (boiling limits 160°-190° C).

EXAMPLE 1 Preparation of1-p-ethoxyphenyl-1-p-propargyl-oxyphenyl-2-nitropropane

45 g of 1-p-ethoxyphenyl-2-nitro-1-propanol and 26.4 g ofphenylpropargyl ether are dissolved in 80 ml of methylene chloride, andthe solution added dropwise at 0° C, with vigorous stirring, to 180 g ofconc. H₂ SO₄ and 20 ml of water. After completion of the addition,stirring is continued for a further hour at room temperature. thereaction mixture is poured on 400 ml of ice water, and twice extractedwith 250 ml of methylene chloride each time. After drying over Na₂ SO₄,the solvent is evaporated off in vacuo, and the crude product dried inhigh vacuum to obtain 60 g of yellow oil (still contains some carbinol).The crude product can be purified by chromatography on silica gel withpetroleum ether containing 5% of ethyl acetate to thus yield 47 g ofpure product in the form of a light-yellow oil having a refractive indexof n_(D) ²⁰ = 1.5654.

The following compounds are prepared in an analogous manner: ##STR8##

EXAMPLE 2 A. Insecticidal stomach poison action

Cotton and potato plants were sprayed with a 0.05% aqueousactive-substance emulsion (obtained from a 10% emulsifiableconcentrate).

After the drying of the resulting coating, Spodoptera litoralis orHeliothis virescens larvae L₃ were placed on the cotton plants, andColorada beetle larvae (Leptinotarsa decemlineata) on the potato plants.The test was carried out at 24° C with 60% relative humidity.

The compounds according to Example 1 exhibited in the above test a goodinsecticidal stomach poison action against Spodoptera litoralis,Heliothis virescens and Leptinotarsa decemlineata larvae.

B. Contact action against stored-food pests and house pests

Five parts by weight of an active substance and five parts by weight oftalcum are mixed together and finely ground. A further 90 parts ofweight of talcum are mixed in to obtain a 5 % dust; this can be used asa starting mixture for 1:1-dilutions for graduated tests of the activesubstances with respect to their action against stored-food pests andhouse pests.

The test insects,

German cockroach (Phyllodromia germanica)

American cockroach (Periplaneta americana)

Russian cockroach (Blatta orientalis),

yellow mealworm imago (Tenebrio molitor) larvae,

larder beetle imago (Dermestes frischii) larvae,

pelt beetle larvae (Attagenus pellio),

European house cricket (Acheta domesticus), and

grain weevil (Sitophilus granarius),

are placed on filter paper in glass dishes, the filter paper having beentreated with 2 g of the 5% formulation. The amount of active substanceis 100 mg of AS/m². The applied 1:1-dilutions then give 2.5%, 1.25%,,0.6%, 0.31% and 0.16% active-substance formulations, which correspond toactive-substance amounts of 50, 25, 12.5, 6.2 and 3.1 mg of AS/m² when 2g of the respective dust formulation is used for each glass dish.

Compounds according to Example 1 exhibited in the above test contactaction against Phyllodromia germanica, Periplaneta americana, Blattaorientalis, Tenebrio molitor, Dermestes frischii, Attagenus pellio,Acheta domesticus and Sitophilus granarius.

C. Contact action against adults of Aedes aegypti

With use of an acetone solution, amounts of 1, 0.1, 0.01 and 0.001 mg ofactive substance per Petri dish were applied. Each test was performedtwice with 10 mosquitoes for each concentration. Both the rate of actionand the applied amount for a 100% mortality were taken into account ineffecting an evaluation.

Compounds according to Example 1 exhibited in the above test afavourable action against adults of Aedes aegypti.

EXAMPLE 3 Action against Chilo suppressalis

Rice plants of the variety Caloro were planted, 6 plants per pot, inplastic pots having a top diameter of 17 cm, and grown to a height ofca. 60 cm. Infestation with Chilo suppressalis larvae (L₁ ; 3-4 mm long)was carried out 2 days after application of the active substance ingranular form (amount applied = 8 kg of active substance per hectare) tothe paddy water. The evaluation of the insecticidal action was made 10days after application of the granules.

Compounds according to EXAMPLE 1 were effective against Chilosuppressalis in the above test.

EXAMPLE 4 Action against ticks

A Rhipicephalus bursa

In each case, five adult ticks or 50 tick larvae were placed into asmall glass tube; the test tubes were then immersed for 1 to 2 minutesin 2 ml of an aqueous emulsion from a diluted series of 100, 10, 1 and0.1 ppm of test substance. The tubes were then sealed with astandardised cotton plug, and inverted so that the active-substanceemulsion could be absorbed by the cotton wool.

An evaluation in the case of the adults was made after 2 weeks, and inthe case of the larvae for 2 days. There were two repeats for each test.

B. Amblyomma hebraeum

With a solution series analogous to that in Test A, tests were carriedout using in each case 20 larvae.

Compounds according to Example 1 were effective in these tests againstadults and larvae of Rhipicephalus bursa and against larvae of Amblyommahebraeum.

What we claim is:
 1. An insecticidal and acaricidal compositioncomprising (1) an insecticidally or acaricidally effective amount of acompound selected from the group consisting of1-p-ethoxyphenyl-1-p-propargyloxyphenyl-2-nitropropane,1-p-isopropylphenyl-1-p-propargyloxyphenyl-2-nitropropane,1-p-isopropylphenyl-1-p-propargyloxyphenyl-2-nitrobutane,1-p-ethylphenyl-1-p-propargyloxyphenyl-2-nitropropane and1-p-ethylphenyl-1-p-propargyloxyphenyl-2-nitrobutane, and (2) an inertcarrier therefor.
 2. A method for combatting insects and acarids whichcomprises applying thereto an insecticidally or acaricidally effectiveamount of 1-p-ethoxyphenyl-1-p-propargyloxyphenyl-2-nitropropane.
 3. Amethod for combatting insects and acarids which comprises applyingthereto an insecticidally or acaricidally effective amount of1-p-isopropylphenyl-1-p-propargyloxyphenyl-2-nitropropane.
 4. A methodfor combatting insects an acarids which comprises applying thereto aninsecticidally or acaricidally effective amount of1-p-isopropylphenyl-1-p-propargyloxyphenyl-2-nitrobutane.
 5. A methodfor combatting insects and acarids which comprises applying thereto aninsecticidally or acaricidally effective amount of1-p-ethylphenyl-1-p-propargyloxyphenyl-2-nitropropane.
 6. A method forcombatting insects and acarids which comprises applying thereto aninsecticidally or acaricidally effective amount of1-p-ethylphenyl-1-p-propargyloxyphenyl-2-nitrobutane.